CN1267676A - Preparation of sulfonated polyether sulfone - Google Patents
Preparation of sulfonated polyether sulfone Download PDFInfo
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- CN1267676A CN1267676A CN 00115419 CN00115419A CN1267676A CN 1267676 A CN1267676 A CN 1267676A CN 00115419 CN00115419 CN 00115419 CN 00115419 A CN00115419 A CN 00115419A CN 1267676 A CN1267676 A CN 1267676A
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- reaction
- sulfonation
- polyethersulfone
- polyether sulfone
- sulphonating agent
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Abstract
Chlorosulfonic acid, which has strong sulfonating capacity, is used as sulfonating agent for homogeneous sulfonation of polyether sulfone. At normal temperature, chlorosulfonic acid can provide reactive electrophilic reagent SO3 to attack the part of benzene ring with relatively high density of electronic cloud and to perform electrophilic substitution, and this makes the sulfonating process with mild and controllable condition easy to operate and makes the sulfonated degree controllable. The excessive solvent is separated and reused for lowering production cost and less environmental pollution. In addition, the said preparation process has less side reaction.
Description
The present invention relates to a kind of preparation method of sulfonated polyether sulfone, relating in particular to a kind of sulphonating agent is the homogeneous phase sulfonation method of chlorsulfonic acid.
Said sulfonated polyether sulfone is called for short SPES, and its structural formula is:
Said sulfonated polyether sulfone is a kind of high performance functional high molecule material, it not only can be used for preparing high temperature resistant ion exchange resin, charged ultra-filtration membrane, charged nanofiltration membrane and charged reverse osmosis membrane, also can be used for preparing medical device that can stand various high-temperature sterilization germicidal treatment etc., this sulfonated polyether sulfone is that the sulfonation by polyethersulfone obtains.
At present, the sulfonation of relevant polysulfones resin such as polysulfones (PSF), phenolphthalein base polyether sulphone (PES-C) has more report, their sulfonation mild condition, easily sulfonation, and the more difficult sulfonation of polyethersulfone (PES), this mainly is in polysulfones (PSF) macromole, has the phenyl ring in the bisphenol-A monomer, and this benzene ring hydrogen more easily is substituted and sulfonation; Owing to contain the phenolphthalein base side chain, coupled benzene ring hydrogen also more easily is substituted and sulfonation in the PES-C macromole; And in the PES macromole, be difficult two kinds of structures, and its sulfuryl (O=S=O) is a strong electron-withdrawing group group, links to each other with phenyl ring to form a stable conjugated system, benzene ring hydrogen activity is reduced and be difficult for being substituted, thereby more difficult sulfonation.
United States Patent (USP) 4,273,903 pairs have following structure (I):
And structure (II):
Multipolymer carried out sulfonation, the result has only structure (II) to be sulfonated, and structure (I) is not sulfonated.United States Patent (USP) 4,413,106 adopt SO
3Make sulphonating agent the PES with structure (I) is carried out the out-phase sulfonation, because this patent is to adopt heterogeneous sulfonation to the sulfonation of polyethersulfone, the ununiformity of its sulfonated bodies is obvious, and react wayward, simultaneously, in entire reaction course, need carry out intensive and stir, equipment requirements is higher, its temperature of reaction low (0 ℃～5 ℃) makes production cost improve therefrom, is unsuitable for the heavy industrialization preparation.
The objective of the invention is to disclose a kind of with chlorsulfonic acid (ClSO
3H) be sulphonating agent, polyethersulfone is carried out the method that the homogeneous phase sulfonated prepares sulfonated polyether sulfone.
Design of the present invention is such:
Because its sulfuryl of polyethersulfone (O=S=O) and coupled phenyl ring form a stable conjugated system, has very strong electrophilic effect, benzene ring hydrogen activity is reduced and be difficult for being substituted, therefore the present invention adopts the chlorsulfonic acid with strong sulfonation ability to make sulphonating agent, and chlorsulfonic acid can be seen SO as
3The complex compound of HCl can provide active electrophilic reagent SO at normal temperatures
3, to attack the higher position of cloud density on the phenyl ring, to carry out electrophilic substitution reaction, thereby sulfonation process is carried out under comparatively gentle condition, side reaction is few, and the hydrogenchloride that generates is removed easily.
According to above-mentioned design, realize that the concrete technical scheme of the object of the invention is as follows:
The general structure of said sulfonated polyether sulfone is as follows:
Wherein: n=90～320; Molecular weight is 20000～80000;
The preparation method of above-mentioned sulfonated polyether sulfone in turn includes the following steps:
(1) polyethersulfone is placed reaction flask, add solvent and under agitation make it dissolve the formation homogeneous system fully, feed N then
2, under 0 ℃～35 ℃ temperature, in above-mentioned homogeneous system, slowly drip a certain amount of sulphonating agent, dropwise the back and keep temperature to continue reaction 0.5～25 hour;
(2) reaction mixture sat layering joins lower floor's reactant in distilled water or the deionized water under 0 ℃～50 ℃, and white fine particle is separated out, and leaves standstill 0.5～24 hour, so that white fine particle is all separated out;
(3) adopt the conventional method purifying from the mixture of step (2) that gets to collect the product sulfonated polyether sulfone, as: filter, with distilled water or deionized water filter cake is washed till neutrality, under 40 ℃～80 ℃ temperature, reduce pressure after draining and dry to constant weight, can obtain sulfonated polyether sulfone, its sulfonation degree scope is 1%-50%.
Said polyethersulfone is the compound with following structural formula:
Wherein: n=90～320; Molecular weight is 20000～80000;
This polyethersulfone is to be formed by a plurality of polyethersulfone monomer link aggregation.
Said sulphonating agent is chlorsulfonic acid (ClSO
3H);
Said solvent comprises the hydrochloric ether and the vitriol oil, wherein preferred methylene dichloride (CH in the hydrochloric ether
2Cl
2), the add-on of solvent there is no strict demand, as long as can make the polyethersulfone dissolving;
The mol ratio of sulphonating agent and polyethersulfone monomer is 1: 1～9: 1 in the sulfonation reaction;
The reaction formula of polyethersulfone monomer sulfonation process is:
The sulfonation reaction temperature is 0 ℃～35 ℃, and optimum temperature range is: 10 ℃～30 ℃; Temperature is too high, will cause the product degradation aggravation, and the sulfonation by product increases, and the too low speed of response that will make slows down, and increases the reaction times.
By controlling the product that reaction conditions can obtain required various sulfonation degree, remaining solvent is recyclable to be recycled, and the HCl of by-product can generate hydrochloric acid after water absorbs.The sulfonation degree of reaction product can be controlled in the present invention, the sulfonation degree of product can be controlled by following factors, i.e. choice of Solvent in the sulfonation reaction, the mol ratio of sulphonating agent and polymer monomer, the dropping time of sulphonating agent, sulfonation reaction temperature and reaction times, and N
2Feed the flow velocity of reactor.
Sulfonation process adopts N
2Protection so not only can prevent the generation of side reaction, and N
2Feeding also can take away the HCl of by-product, after water absorbs, can obtain by-product hydrochloric acid.
Related sulfonated products when the product sulfonation degree is low, is 1～13% o'clock as sulfonation degree in precipitation process, and the white solid of separating out is the macrobead shape, uses distilled water (or deionized water) to be washed till neutrality again after needing to be crushed to it to a certain degree; Or reacted mixing liquid is injected in the distilled water, obtain the powdered products composition granule.
By above-mentioned disclosed technical scheme as seen, the said method of the present invention can at room temperature be carried out the reaction conditions gentleness, easy and simple to handle, be easy to control, and sulfonation degree can control, remaining solvent can be recycled through separation, not only production cost is low, and environmental pollution is little, and therefore, present method is a kind of preparation method who is easy to industrialized sulfonated polyether sulfone.
Below will do detailed explanation to details of the present invention by embodiment.
Embodiment 1
Get 8g (0.345mol) polyethersulfone (PES, Jilin University demonstration plant), its structural formula is:
Molecular weight is 30000.
The four-hole boiling flask of being with stirring, prolong, thermometer etc. is put in 70 ℃ of oven dry 24 hours of reducing pressure down, adds the methylene dichloride of 80ml, it is dissolved fully, at N
2Protection in 25 ℃ of slow 11.7ml (0.176mol) chlorsulfonic acids that drip in solution, dropwised in 90 minutes down, continued reaction 150 minutes, and sulfonation finishes.With the reaction mixture sat layering, lower floor's reactant is injected in 30 ℃ of distilled water that add stirring, leaves standstill 24 hours, leach product with sand core funnel, and product is washed till neutrality, drain back decompression under 70 ℃ and dry to constant weight with distilled water, getting product is 9.3 grams, sulfonation degree (DS)=40%.
Embodiment 2
Get 8g (0.345mol) as said polyethersulfone in the example 1, molecular weight is 50000,70 ℃ of oven dry 24 hours of reducing pressure down, puts into four-hole boiling flask, adds the methylene dichloride of 80ml, it is dissolved fully, at N
2Protection in 25 ℃ of slow 7ml (0.105mol) chlorsulfonic acids that drip in solution, dropwised in 90 minutes down, continued reaction 150 minutes, and sulfonation finishes.With the reaction mixture sat layering, lower floor's reactant is injected in 30 ℃ of deionized waters that add stirring, leaves standstill 24 hours, with the sand core funnel filtration and with deionized water product is washed till neutrality, drain back decompression under 70 ℃ and dry to constant weight, getting product is 8.6 grams, sulfonation degree (DS)=16%.
Embodiment 3
Get 8g (0.345mol) as said polyethersulfone in the example 1, four-hole boiling flask is put in 70 ℃ of oven dry 24 hours of reducing pressure down, adds the methylene dichloride of 80ml, it is dissolved fully, at N
2Protection in 20 ℃ of slow 16.34ml (0.2457mol) chlorsulfonic acids that drip in solution, dropwised in 90 minutes down, continued reaction 150 minutes, and sulfonation finishes.Reaction mixture is being added 30 ℃ of distilled water of stirring, is leaving standstill after 24 hours with sand core funnel and filter and product is washed till neutrality with distilled water, drain the back 70 ℃ down decompression dry to constant weight, product is 8.8 grams, sulfonation degree (DS)=23.4%.
Embodiment 4
Change chlorsulfonic acid consumption among the embodiment 1 into 7ml (0.105mol), temperature of reaction changes 15 ℃ into, and then obtaining product is 8.4 grams, DS=9.6%.
Embodiment 5
Use solvent among the embodiment 1 instead the vitriol oil (98%), the chlorsulfonic acid consumption is 11.7ml (0.176mol), and temperature of reaction is 20 ℃, and the reaction times is 22 hours, and then obtaining product is 9.2 grams, DS=37.4%.
Claims (5)
1. the preparation method of a sulfonated polyether sulfone is characterized in that in turn including the following steps:
(1) is dissolved in polyethersulfone in the solvent and places reaction flask, under 0 ℃～35 ℃ temperature, add sulphonating agent, finish, continue reaction 0.5～25 hour;
(2) with the reaction mixture sat layering, lower floor's product joins 0 ℃～50 ℃ distilled water or deionized water, and white fine particle is separated out;
(3) adopt conventional method from above-mentioned mixture, to collect the said sulfonated polyether sulfone of purifying;
Said polyethersulfone is the compound with following structural formula:
Wherein: n=90～320;
Molecular weight is 20000～80000;
Said sulphonating agent is a chlorsulfonic acid;
Said solvent is the hydrochloric ether or the vitriol oil;
The mol ratio of sulphonating agent and polyethersulfone monomer is 1: 1～9: 1.
2. the method for claim 1 is characterized in that, the sulfonation reaction temperature is 10 ℃～30 ℃.
3. the method for claim 1 is characterized in that, said hydrochloric ether is a methylene dichloride.
4. the method for claim 1 is characterized in that, said sulphonating agent is slowly to add.
5. as the arbitrary described method of claim 1～4, it is characterized in that reaction process is at N
2Protection is carried out down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00115419 CN1267676A (en) | 2000-04-21 | 2000-04-21 | Preparation of sulfonated polyether sulfone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00115419 CN1267676A (en) | 2000-04-21 | 2000-04-21 | Preparation of sulfonated polyether sulfone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504257A (en) * | 2011-11-30 | 2012-06-20 | 杭州北斗星膜制品有限公司 | Preparation method of sulfonated polyethersulfone for preparing macromolecule separation films |
| CN103788376A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Carboxyl-containing polyethersulfone, reverse osmosis membrane, and preparation methods of the carboxyl-containing polyethersulfone and the reverse osmosis membrane |
| CN104759213A (en) * | 2014-09-25 | 2015-07-08 | 张一琛 | Preparation method of polymer charged porous membrane |
| CN111116914A (en) * | 2019-12-26 | 2020-05-08 | 白银图微新材料科技有限公司 | Synthesis method for preparing sulfonated poly (amino) sulfate by using poly (amino) sulfate polymer as raw material |
-
2000
- 2000-04-21 CN CN 00115419 patent/CN1267676A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504257A (en) * | 2011-11-30 | 2012-06-20 | 杭州北斗星膜制品有限公司 | Preparation method of sulfonated polyethersulfone for preparing macromolecule separation films |
| CN103788376A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Carboxyl-containing polyethersulfone, reverse osmosis membrane, and preparation methods of the carboxyl-containing polyethersulfone and the reverse osmosis membrane |
| CN103788376B (en) * | 2012-10-29 | 2017-04-26 | 中国石油化工股份有限公司 | Carboxyl-containing polyethersulfone, reverse osmosis membrane, and preparation methods of the carboxyl-containing polyethersulfone and the reverse osmosis membrane |
| CN104759213A (en) * | 2014-09-25 | 2015-07-08 | 张一琛 | Preparation method of polymer charged porous membrane |
| CN111116914A (en) * | 2019-12-26 | 2020-05-08 | 白银图微新材料科技有限公司 | Synthesis method for preparing sulfonated poly (amino) sulfate by using poly (amino) sulfate polymer as raw material |
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